Magenta-colored cyan-forming couplers



United States Patent 3,034,892 MAGENTA-COLORED CY AN -FORMDIG C U L SRonald J. Gledhill and John Williams, Rochester, N.Y., assignors toEastman Kodak Company, Rochester, N .Y., a corporation of New Jersey NoDrawing. Filed 0ct. 2 7, 19.58, Ser. No. 769,552 12 Claims. (CI. 96-55)This invention relates to color photography and particularly to coloredcouplers for use in photographic processes.

Color-forming compounds which react during photographich developmentwith the development product of aromatic amino developing agents to formcolored images are well known. Generally, these color-forming compoundsare colorless or substantially colorless. This lack of color is usually,desirable when the. coupler is to be incorporated in the emulsion layerand the unused coupler remains after formation of the colored image.

Couplers which are in themselves more or less strongly colored and whichcontain a chromophore group which is split off or destroyed during andby means or the cou pling reaction with the result that. the originalcolor of thecoupler is destroyed and a. new dye is formed upon couplingare disclosed in Glass, Vittumyand. Weissberger U.S. Patents 2,453,661,Noverrrber 9, 1948; 2,455,169, November 30, 1948; 2,455,170, November30, 1948; 2,521,908, September 12, 1950; and Graham U.S. 2,706,684,April 19, 1955,

Upon development of an emulsion layer containing one of these coloredcouplers, the coupler color is destroyed and a new color is formed bythe couplingreaction at those points where development occurs. There isformed in this way a dye image, consisting of the new dye and theresidual colored coupler. The theory of color correction requires thatthe sum of the absorption of the residual colored coupler and theundesired absorption of the image dye should be nearly constant.

In order to correct for color deficiencies of the cyan dye produced uponcolor development, it isdesirable to have magenta-colored couplers withhigh green-absorption relative to the blue-absorption and nored-absorption. This is especially true where overcorrection is desired.This requirement is not. always fulfilled by colored couplers of priorart.

In U.S. Patent 2,521,908, are described l-hydroxy-Z- naphthamide coloredcoupler compounds having the q ula;

in which X is hydrogen or alkyl, Y is. a mononuclear aryl radical, or anaralkyl radical and R is a mononuclear aryl radical. All the compoundsdescribed in this patent are yellow to orange-red in color, rather thanthe desired magenta color.

In U.S. Patent 2,706,684 are described l-hydroxy-Z- naphthanilidecolored coupler compounds having the above formula in which X ishydrogen, Y is a mononuclear aryl radical substituted in a positionortho to the amido group with either halogen, allcoxy or mononucleararyloxy radicals and R is a mononuclear aryl radical. Most of thesecoupler compounds have the desired magenta color. However, since thiscolor depends upon 3,034,892 Patented May 15, 1962 the presence of-a.substituent inan ortho position on the anilide nucleus, the cyan dyeproduced during color development must also contain this nucleus.Although such compounds are useful, there are instances where thisrestriction of the type of cyan dye which can be produced would beobjectionable. For instance, the dyes produced by color development ofthe colored couplers described in the above patent are greenish ratherthan cyan in color, since their absorption maxima arewell in theinfrared.

It is therefore an object of the present invention to providemagenta-colored cyan-forming couplers which will make. it possibletocorrect for the color deficiencies in the cyan dye produced upon colordevelopment. A further object is to provide couplers which are not onlymagentaecolored but which are significantly less restricted than priorart compounds with respect to the types of cyan dyes which can beproduced by means of photographic color development. A further object isto provide magenta-colored cyan-forming couplers which demonstrateunusually large bathochromic shifts, that are unexpected in View of thesmall chemical difierences from other couplers. A further object is toprovide a magentacolored cyan-forming coupler which will overcorrect forthe deficiencies inthe cyan dye produced upon color development. A stillfurther, object is to provide non-diffusing magenta-colored cyan-formingcouplers which can be used in combination with uncolored cyan-formingcouplers in photographic silver halide. emulsions to correct'for thecolordeficiencies in the cyan dye produced upon color development. Otherobjects will appear from the. following description and claims.

These and other objects are accomplished by means. of this invention byusing magenta-colored cyan-forming couplers which we have discovered.These new couplers all have a nucleus consisting of a l-hydroxynaphthamide with an oxaralkyl, an alkyl, an aryl, or an aryloxphenylsubstituent on the amide group and an azo lgroup substituent para to thehydroxyl. This common nucleus is connected either to a l-phenyl-Z-ketogrouping or to a Z-naphthyl-B carbalkoxy group. These couplers are notonly magenta-colored but all have a max of at least 500 m anddemonstrate unusually large bathochrornic shifts from prior artcouplers. These bathochromic shifts are unexpected in view of the smallchemical dilferences between our couplers and the non-magenta-coloredcyanforming couplers known before. These couplers are not onlymagenta-colored but give much more freedom than prior art compoundsbecause of the types of cyan dyes which can be produced from them duringcolor development. Our couplers which have an alkyl, aryloxyalkyl, oralkyl substituted aryloxyalkyl radical attached to their amido groupproduce dyes upon color development that are truly cyan in color.

The preferred embodiments of this invention are magenta-coloredcyan-forming coupler compounds selected from the group consisting ofcompounds. with the general formulas:

wherein X is an integer in the range of -4; Y is 0 or 1; R is a memberselected from the group consisting of phenyl radicals, alkyl radicalshaving from 6 to 15 carbon atoms, alkyl-substituted phenyl radicals andalkylsubstituted phenoxy phenyl radicals; R is an alkyl group of 1-4carbon atoms in either straight or branched chains; and R is an alkylgroup having 1 to 12 carbon atoms in either straight or branched chains.

The alkyl substituents on the phenyl and phenoxyphenyl radical of R canbe varied widely in size however they usually have from 1 to 15 carbonatoms.

I The azo group attached to the active carbon which is para to thenaphtholic hydroxyl group is split off or removed by the oxidizeddeveloper when the azo-substituted coupler is treated with the oxidizeddeveloper either in aqueous solution or in a light-sensitivephotographic element. Thus, the coupler can be converted to a diiferent-1y colored compound and the azo group readily removed from it by meansof reaction with the oxidized developing agent. Although the exactmechanism of this reaction is not completely understood, the reactionappears to proceed as follows:

0 ONE-Q N ll ture with uncolored couplers which appear to react asfollows:

CONE

to form the same dye as is formed from the colored coupler.

Typical compounds embodying the invention and which can be usedaccording to our invention include 5 the following which illustrate theinvention but to which the invention is not limited:

COMPOUND I t w Q N it 1-hydroxy-4-(2-acetyl phenylazo)-2-naphthani1ide[Melting po1nt231-232 0.]

Composition Calculated Found C- 73. 4 73. 6 H 4. 6 4. i N 10. 3 10. 2

COMPOUND II O (L.IENH(CH2)4O C5H11-t sHu-t N it 0 i i-0H,

1-hydroxy-4- (2-acety1 phenylazo) -N- [6-2,4-dl-tertlary-amylphenoxy)buty11-2-naphthamide 1-hydroxy-4-2-pr0piouy1 phenylazo) -N [6- (2,4-di-tertiary-amylphenoxy)butyl1-2-naphthamide [Melting point144-145 0.]

Composition Calculated Found C. 75. 6 75. 6 H 7. 7 7. 3 N 6. 6 6. 6

COMPOUND X i (ll-O Cums-n 1-hydroxy-4 (3 car-bododecoxy-2-naphthylazo)-N-[4-(2,4-dltertiary-amylphenoxy) phenyl] -2-naphthami de [Meltingpolnt117119 0.]

Composition Calculated Found 78.1 78.. F 7.8 H .729 N 4.9 V 5.3

The objects of'this invention can be accomplished with other coloredcoupler compounds as defined herein having a nucleus of1-hydroxy-4-phenylazo-2-naphthamide with other aryl, alkyl, aryloxyalkylor aryloxyphenyl radicals substituted on the amide and other keto groupssusbtitute'don thecar'boiatthe 2-position of the phenylazo group, orwith other colored couplers as defined herein having a nucleusconsisting of 1-hydroxy-4-(2- naphthylazo)-2-naphthamide with otheralkyl, aryl, aryloxyalkyl or aryloxyphenyl radicals substituted on theamide and other carbalkoxy or acylgroups substituted on the carbon inthe 3rd position on the Z-naphthylazo group. All of these compounds havethe common characteristic of being magenta-colored before developmentand forming a cyan dye upon development.

All of these compounds are further characterized by the unexpectedbathochromic shift they demonstrate which makes them valuable for colorcorrection in photographic silver halide emulsions.

The preferred colored coupler compounds of this invention have a A of atleast 500 mu. Typical A Our couplers show unusually and unexpectedlylarge bathochromic shifts from corresponding coupler compounds having acarbalkoxy group on the carbon in the two position on the phenylazo partof the nucleus and are, therefore, superior for correcting the colordeficiencies of the cyan dye formed by color development. This isillustrated by the bathochromic shift of 13 mp shown between the) valuefor Compound IV and the corresponding carbalkoxy derivative1-hydroxy-4-(2-carbopropoxy phenylazo) -N-[52,4-di-tertiaryamylphenoxy)butyl]-2-naphthamide. This is further illustrated by thebathochromic shift of 32mg shown between the A value for Compound VIIand the-coupler 1-hydroxy-4-(2- carbobutoxy phenylazo)-N'-[6-2g4-di-tertiary amylphenoxy)-buty1]-2-naphthamide.' The very largebatho'chro- .may be prepared by any suitable method such as the reactionof the 1-hydroxy-2-naphthamide with the appropriate diazonium chloridecompound. Equal molar quantities of the l-hydroxy-Z-naphthamide andaminehydrochloride are used. A 10% excess of NaNO over the equal molaramount is used to prepare the diazonium chloride from theaminehydrochloride.

Compound I is prepared as follows:

n: ooNHorH, Q-mm The l-hydroxy-Z-naphthanilide (13.2 g., 0.05 mole) isdissolved in 200 ml. pyridine and the solution chilled in an ice bath.O-amino acetophenone hydrochloride (8.6 g., 0.05 mole) is dissolved in50 ml. 10% hydrochloric acid and the solution chilled to 0 C. Sodiumnitrite (3.9 g., 0.05 mole+ 10% excess) is dissolved in 5 ml. H 0 andadded to the chilled acid solution. After 30 minutes, sulfamic acid isadded to the diazonium solution to remove excess sodium nitrite and thediazonium solution is added to the chilled pyridine solution withstirring. After several hours the dye is collected, washed well with H 0and dried. The dye is recrystallized from one liter glacial acetic acid.A yield of 13.5 g. was obtained by'using this procedure.

Compound H is prepared by the following procedure. Commercial2,4-tertiary-di-amylphenol and 'y-chlorobu tyronitrile are condensed inthe presence of alkali. The resultant-2,4-tertiary-di-amylphenoxybutyronitrile is reduced to6-2,4-tertiary-di-amylphenoxybutylamine and the amine condensed with anequivalent amount of 1- naphtho'l-Z-carboxylic acid phenyl ester to givel-hydroxy N [6(2,4 ditertiary-amylphenoxy) n-buty1]-2- naphthamide. Thisnaphthamide (38. g., 0.08 mole) is dissolved in 200 ml. pyridine and thesolution chilled in an ice bath. O-amino-aceto phenone hydrochloride(13.7 g., 0.08 mole) is dissolved in 50 ml. of 10% hydrochloric acid,the solution is chilled to 0 C. and sodium nitrite (6.1 g., 0.088 mole)dissolved in 25 ml. H O is added. After 30 minutes the excess sodiumnitrite is removed with sulfamic acid. The diazonium solution is slowlyadded to the pyridine solution and after several hours 1500 ml. H O isadded. The dye is collected and washed well with H O. After drying, thedye is recrystallized from 1500 ml. of acetonitrile twice. A yield of33. g. was obtained by using this procedure.

Compounds HI, IV, and V are prepared in the same,

manner as Compound II using the couplers and diazonium salts listed inTable II. Compound V is purified by recrystallization from butanol inplace of the acetonitrile used for Compound 11.

tiary-butylphenoxy)-phenyl]- diazonium chloride. Z-naphthamide.

Compound V1 is prepared by the following procedure.

Ethyl-3-aniino-2-naphthoate (28. g., 0.13 mole) dissolved in 100 m1.glacial acetic acid is added with stirring to a mixture of 100 ml.concentrated hydrochloric acid and 100" g. of ice. A solution of sodiumnitrite (10. g., 0.13 mole'+10% excess) in 25 ml. H O is added to theacid solution. After 30'minutes in an ice bath, sulfamic acid is addedto remove excess sodium nitrite. This diazonium solution is added withstirringto an icechilled solution of the naphthamide dissolved in 500ml. of pyridine. H O is added and the dye is collected, washed well withH and dried. The product, coupler Compound VI, is recrystallized fromone liter of butanol. A yield of 79. g. was obtained by using thisprocedure.

Compounds VII and VIII are prepared in the same manner as Compound VIusing the couplers and diazonium salts shown in Table III. N propanol,and 1:1 dioxane: ethanol are the solvents used to recrystallizeCompounds VII and VIIIrespectively in place ofbutanol.

Compound IX is prepared by the following procedure.

'The 3-carbolauroxy-2-naphthylamide (2.37 g., 0.0067 mole) is slurriedin 20 ml. glacial acetic acid at room temperature and 20 ml.hydrochloric acid added; Sodium nitrite (0.52 g., 0.0075 mole) dissolvedin 5' ml. H 0 and a small amount of ice are added to the hyd'rochloridemixture. This mixture is stirred in an ice bath for 30 minutes afterwhich the excess sodium nitrite is destroyed with sulfamic acid. Thediazonium solution is added with stirring to an ice chilled solution ofthe naphthamide (3.16 g., 0.0067 mole) dissolved in 25 ml. of pyridine.Coupler Compound IX, the product, is collected after several hours andrecrystallized from n-pro-- panol. A yield of 3.6 g. was obtained.

Compound X is prepared in the same manner as Compound IX by reacting1-hydroxyN-[4-(2,4-di-tertiaryamylphenoxy)-phenyl]-2-naphthamide with 3carbol'auroxy-2-naphthylene diazonium chloride.

Our compounds can be incorporated either in a developer solution or inthe emulsion layer of photographic material according to their intendeduse and diffusion characteristics. They can be used in any photographicsilver halide emulsion where. cyan-forming couplers are used. Apreferred use is in an. emulsion layer of either a single or amultilayer color photographic material in order to secure colorcorrection by masking effects described in Hanson US. Patent 2,449,966.The Hanson process involves the color correction method in which acolored color-forming coupler is incorporated in the photographicemulsion layer prior to exposure and upon development is converted to adifferently colored image where the layer was exposed. The couplerremaining in the unexposed portion of the layer retains its originalcolor and by a suitable choice of the color of the original Afterstanding several hours 500 ml. off

10 coupler and the color of the final dyeimage, a masking or colorcorrection effect can be obtained. The compounds of this inventionprovide colored couplers which are magenta-colored and still form thedesired cyan image.

Our magenta-colored cyan-forming coupler compounds can be used alone orin conjunction with uncolored cyantorming couplers to control theamount, of correctionor,

overcorrection produced by the masking process. The use of colored withuncolored couplers is, described in Vittum et al. US. Patent 2,428,054,September 30, 1947. Usually when uncolored and colored couplers are usedtogether for correction masking, a colored coupler is selected whichforms an image of the same dye or a dye of the same hue as the image dyeformed with the uncolored coupler upon coupling with the developmentproduct of a color developer such as a primary aromatic amino developingagent. lhe relative proportions of the colored and uncolored couplersused in the mixture can be readily determined from spectral absorptioncurves or from densitometric curves as illustrated by Vittum et al.

In general when our colored couplers are used with un-- colored couplersrather than being used alone, they will be used in an amount between 10%and 70% of the 0.15 gram of l-hydroxy-N-[6-(2,4-di-tertiary-amylphenoxy)butyl]-2-naphthamide and 0.19 gram ofl-hydroxy-4-(2-acetylphenylaco) N' 1[6-(2,4-di-tertia1'yamylphenoxy)-butyl]-2-naphthamide, coupler CompoundII, were dissolved in 0.67 gram of tri-o-cresyl phosphate by heating toabout C. with stirring. This solution was intimately mixed with anddispersed in one containing 17.7 ml. of 10% gelatin and 2.0 ml. of 5%alkanol B'. The dispersion was mixed at 40 C. with 12.5 ml. of a meltednegative speed silver :bromoiodide emulsion, 1.5 ml. of 7.5% saponin wasadded. and the mixture was coated on a cellulose acetate support. Afterdrying, the coating was exposed under an image and developed for 10minutes in a 2-amino-5-diethylaminotoluene developing composition of thefollowing formula to, form a silver and cyan dye image:

The film was then treated in a conventional acid stop bath for'fiveminutes, washed for five minutes. The silyer image and residual silverhalide were removed by (l) treating five minutes in a potassiumferricyanidepotassium bromide bleach, (2) washing for five minutes and(3) fixing for five minutes in a hypo fixing bath. The film was given afinal wash for ten minutes. The result was a negative cyan dye imagehaving maximum absorption at a wavelength of 694 mg and in the unexposedareas a masking colored coupler image having a maximum absorption at aWavelength of 508 m Example II A multilayer color film was made asfollows using emulsion melts made in a manner similar to that describedin the single layer example above:

(1) A gelatin dispersion of a yellow coupler, whenzoyl-4-[a-(2,4 ditertiary-amylphenoxy) acetamido] -2- methoxyacetanilide dissolved indi-n-butylphthalate, was added to a blue-sensitive gelatin silver halideemulsion and coated as the bottom layer,

(2) A gelatin interlayer,

. (3) A gelatin dispersion of cyan coupler, l-hydroxy- N-[6-(2,4di-tertiary amylphenoxy)butyl] 2 naphthamide and Compound H,1-l1ydroxy-4-(2-acetylphenylazo)-N-[6 (2,4 di tertiaryamylphenoxy)butyl] 2- naphthamide dissolved in tri-o-cresylphosphate,was added to a red-sensitive silver halide emulsion, and coated as thethird layer,

(4) A gelatin interlayer was coated as the fourth layer,

A gelatin dispersion of magenta coupler,l-(ptertiary-butylphenoxyphenyl)-3 a(p-tertiarybutylphenoxy)propionyl-amino-S-pyrazolone, and coloredmagenta coupler, 1(p-tertiary-butylphenoxyphenyl)-3-a-(ptertiarybutylphenoxy)propionylamino 4 (p-methoxyphenylazo)-5-pyrazolone, dissolved intri-o-cresylphosphate, was added to a green-sensitive silver halideemulsion and coated as the top sensitive layer. The film was exposed andprocessed in the same manner as the single layer material above to yielda color-corrected three color dye image.

Example III V 0.35 gram of l-hydroxy-4(2-acetylphenylazo)-N-[6-(2,4-ditertiary amylphenoxy)butyl] 2 naphthamide, coupler Compound II,was dissolved in 0.70 gram of trio-cresyl phosphate by heat to about 120C. with stirring. ljhis solution was intimately mixed with and dispersedin one containing 17.7 ml. of gelatin and 2.0 ml. of 5% alkanol B. Thedispersion was mixed at 40 C. with 12.5 ml. of melted negative speedsilver bromoiodide emulsion, 1.5 ml. of 7.5 sapom'n was added, and themixture was coated on a cellulose acetate support. After drying, thecoating was exposed under an image and developed for 10 minutes in thedeveloper composition defined in Example I. The film was then treated ina conventional acid short stop bath for 5 minutes, and washed for 5minutes. The silver image and residual silver halide were removed by theprocedure described in Example I. The result was a negative cyan dyeimage having maximum absorption at a wavelength of 694 my. and in theunexposed areas a masking colored coupler image having a maximumabsorption at a wavelength of 508 mg.

The color developing agents used for development of emulsion layerscontaining our couplers or for the devevlopment of emulsion layers inthe presence of our couplers include the well-known primary aromaticamino silver halide developing agents such as the phenylenediaminesincluding the alkyl phenylene diamines and alkyl toluene diamines..These developing agents are usually used in the salt form such as thehydrochloride or sulfate which is more stable than the amine. Thep-aminophenols and their substitution products may also be used wherethe amino group is unsubstituted. The N-alkyl sulfonamidoalkyl-p-phenylenediamine agents of U.S. Patent 2,193,015 are also veryuseful. All of the de- Velopirrg agents have an unsubstituted aminogroup which enables the oxidation product of the developer to couplewith the color-forming compounds that form a dye image.

. 'l he couplers of our invention are used in photographic emulsions ofthe developing out type.

The emulsions can be chemically sensitized by any of the acceptedprocedures. The emulsions can be digested with naturally active gelatin,or sulfur compounds can be added such as those described in SheppardU.S. Patent 1,574,944; Sheppard and Punnett U.S. Patent 1,623,499; andSheppard and Brigham U.S. Patent 2,410,689. H

The emulsions can also be treated with salts of the noble metals such asruthenium, rhodium, palladium,

iridium, and platinum. Representative compounds are ammoniumchloropalladate, potassium chloroplatinate, and sodium chloropalladite,which are used for sensitizing in amounts below that which produces anysubstantial fog inhibition, as described in Smith and Trivelli U.S.Patent 2,448,060, and as antifoggants in higher amounts, as described inTrivelli and Smith U.S. Patents 2,566,245 and 2,566,263. 3

The emulsions can also be chemically sensitized with gold salts asdescribed in Waller, Collins, and Dodd U.S. Patent 2,399,083 orstabilized with gold salts as described in Damschroder U.S. Patent2,597,856 and Yutzy and Leermakers U.S. Patent 2,597,915. Suitablecompounds are potassium chloroaurite, potassium aurithiocyanate,potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazolemethochloride.

The emulsions can also be chemically sensitized with reducing agentssuch as stannous salts (Carroll U.S. Patent 2,487,850), polyamines, suchas diethylene triamine (Lowe and Jones U. S. Patent 2,518,698),polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,- 925 orbis(,B-aminoethyl) sulfide and its water-soluble salts (Lowe and JonesU.S. Patent 2,521,926).

The emulsions can also be optically sensized with cyanine andmerocyanine dyes, such as those described in Brooker U.S. Patents1,846,301; 1,846,302; and 1,942,- 854; White U.S. Patent 1,990,507;Brooker and White U.S. Patents 2,112,140; 2,165,338; 2,493,747; and2,739,- 964; Brooker and Keyes U.S. Patent 2,493,748; Sprague U.S.Patents 2,503,776 and 2,519,001; Heseltine and Brooker U.S. Patent2,666,761; Heseltine U.S. Patent 2,- 734,900; VanLare U.S. Patent2,739,149; and Kodak Limited British Patent 450,958.

The emulsions can also be stabilized with the mercury compounds ofAllen, Byers, and Murray U.S. Patent 2,728,663; Carroll and Murray U.S.Patent 2,728,664, and Leubner and Murray U.S. Patent 2,728,665; thetriazoles of Heimbach and Kelly U.S. Patent 2,444,608; the azaindenes ofHeimbach and Kelly U.S. Patents 2,- 444,605 and 2,444,606; Heimbach U.S.Patents 2,444,- 607 and 2,450,397; Heimbach and Clark U.S. Patent 2,-444,609; Allen and Reynolds U.S. Patents 2,713,541 and 2,743,181;Carroll and Beach U.S. Patent 2,716,062; Allen and Beilfuss U.S. Patent2,735,769; Reynolds and Sagal U.S. Patent 2,756,147; Allen and SaguraU.S. Pat ent 2,772,164, and those disclosed by Birr in the Z. wiss.Phot. 47 2 (1952); the quaternary benzothiazolium compounds of Brookerand Staud U.S. Patent 2,131,038; and 1111625 zinc and cadmium salts ofJones U.S. Patent 2,839,-

The emulsions may also contain speed-increasing compounds of thequaternary ammonium type of Carroll U.S. Patent 2,271,623; Carroll andAllen U.S. Patent 2,288,226; and Carroll and Spence U.S. Patent2,334,864; and the polyethylene glycol type of Carroll and Beach U.S.Patent 2,708,162.

The emulsions may contain a suitable gelatin plasticizer such asglycerin; a dihydroxy alkane such as 1,5- pentane diol as described inMilton et al. U.S. Serial No. 588,951, filed June 4, 1956 now U.S.Patent 2,960,404, issued November 15, 1960; an ester of an ethylenebisglycolic acid such as ethylene bis(methyl glycolate) as described inMilton U.S. Serial No. 662,564, filed May 31, 1957 now U.S. Patent2,904,434, issued September 15, 1959; bis-(ethoxy diethylene glycol)succinate as described in Gray U.S. Serial No. 604,333, filed August 16,1956 now U.S. Patent 2,940,854, issued June 14, 1960 or a polymerichydrosol as results from the emulsion polymerization of a mixture of anamide of an acid of the acrylic acid series, an acrylic acid ester and astyrenetype compound as described in Tong U.S. Serial No. 311,319, filedSeptember 24, 1952 now U.S. Patent 2,- 852,386, issued September 16,1958. The plasticizer may be added to the emulsion before or after theaddition of a sensitizing dye, if used.

The emulsion may be hardened with any suitable hardener for gelatin suchas formaldehyde; a halogen-substituted aliphatic acid such as mucobromicacid as described in U.S. Patent 2,080,019 of White; a compound having aplurality of acid anhydride groups such as 7,8-diphenylbicyclo(2,2,2) 7octene 2,3,5,6 tetracarboxylic dianhydride, or a dicarboxylic or adisulfonic acid chloride such as terephthaloyl chloride ornaphthalene-1, S-disulfonyl chloride as described in U.S. Patents2,725,294 and 2,725,295 of Allen and Carroll; a cyclic 1,2-diketone suchas cyclopentane-1,2-dione as described in U.S. Patent 2,725,305 of Allenand Byers; a bisester of methanesulfonic acid such as1,2-di-(methanesulfonoxy)-ethane as described in U.S. Patent 2,726,162of Allen and Laakso; l,3-dihydroxymethylbenzimidazole-Z-one as describedin U.S. Patent 2,732,316 of July, Knott and P01- lak; a dialdehyde or asodium bisulfite derivative thereof, the aldehyde groups of which areseparated by 2-3 carbon atoms such as 3-methyl glutaraldehyde bis-sodiumbisulfite as described in U.S. application Serial No. 556,- 031 of Allenet al., filed December29, 1955; a bis-aziridine carboxamide such astrimethylene bis(l-aziridine carboxamide) as described in Allen et a1.U.S. Serial No. 599,891, filed July 25, 1956 now U.S. Patent 2,950,-197, issued August 23, 1960; or 2,3-dihydroxy dioxane as describedin-Jeff reys U.S. Serial No. 624,968, filed November 29, 1956 now U.S.Patent 2,870,013,, issued January 20, 1959;

The emulsions may have been suppliedwith a coating aid such as saponin;a lauryl or oleyl monoether of polyethylene glycol as described in U.S.Patent 2,831,766 of Knox and Davis; a salt of a sulfated and alkylatedpolyethylene glycol ether as described in U.S. Patent 2,719,- 087 ofKnox and Davis; an acylated alkyl taurine such as the sodium salt ofN-oleoyl-N-methyl taurine as described in U.S. Patent 2,739,891 of Knox,Twardokus, and Davis; the reaction product of a dianhydride oftetracarboxybutane with an alcohol or an aliphatic amine containing from8 to 18 carbon atoms which is treated with a base, for example, thesodium salt of the monoester of tetracarboxybutane as described in Knoxet al. U.S. Serial No. 485,812, filed February 2, 1955 now U.S. Patent2,843, 487, issued July 15, 1958; a water-soluble maleopimarate or amixture of a water-soluble maleopimarate and a substituted glutamatesalt as described in U.S. Patent 2,823,123 of Knox and Fowler; an alkalimetal salt of a substituted amino acid such as disodiurnN-(carbo-p-tert. octylphenoxypentaethoxy) glutamate as described in Knoxet al. U.S. Serial No. 600,679, filed July 30, 1956; or asulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyD-N-octadecylsulfosuccinamate or N-lauryl disodium sulr'osuccinamate as described inKnox et al. U.S. Serial No. 691,125, filed October 21, 1957 now U.S.Patent 2,992,108, issued July 11, 1961.

The couplers which we have described may be used in various kinds ofphotographic emulsions. Various silver salts may be used as thesensitive salt such as silver bromide, silver iodide, silver chloride ormixed silver halides such as silver chlorobromide or silver bromoiodide.The

couplers can be used in emulsions of the mixed-packet type, such asdescribed in Godowsky U.S. Patent 2,698,- 794 or emulsions of themixed-grain type, such as described in Carroll and Hanson U.S. Patent2,592,243. These couplers can also be used in emulsions which formlatent images predominantly on the surface of the silver halide crystalor in emulsions which form latent images predominantly inside the silverhalide crystal, such as those described in Davey and Knott U.S. Patent2,592,- 250.

In the preparation of the silver halide dispersions employed forpreparing silver halide emulsions there may be employed as thedispersing agent for the silver halide in its preparation, gelatin orsome other colloidal material such as colloidal albumin, a cellulosederivative, or a synthetic resin, for instance, a polyvinyl compound.

14 Some colloids which maybe used as polyvinyl alcohol or a hydrolyzedpolyvinyl acetate as described in U.S. Patent 2,286,215 of Lowe; a farhydrolyzed cellulose ester such as cellulose acetate hydrolyzed to anacetyl content of 1926% as described in U.S. Patent 2,328,808 of Loweand Clark, a water-soluble ethanolamine cellulose acetate as describedin U.S. Patent 2,322,085 of Yutzy; a polyacrylamide having a combinedacrylamide' content of 30-60% and a specific viscosity of 0.25-1.5' oran imidized polyacrylamide of like acrylamide content and viscosity asdescribed in U.S. Patent 2,541,474 of Lowe, Minsk and Kenyon; zein asdescribed in-U.S. Patent 2,563,791 of Lowe; a vinyl alcohol polymercontaining urethane carboxylic acid groups of the type described in U.S.Patent 2,768,154 of Unruh and Smith, or containing cyanoacetyl groupssuch as the vinyl alcohol-vinyl cyanoacetate copolymer as described inU.S. Patent 2,808,331 of Unruh, Smith, and Priest; or a polymericmaterial which results from polymerizing a protein or a saturatedacylated protein with a monomer having a vinyl group as described inIllingsworth U.S. Serial No. 527,872, filed August 11, 1955, now U.S.Patent 2,852,382, issued September 16, 1958.

If desired, compatible mixtures of two or more of these colloids may beemployed for dispersing the silver halide in its preparation.

The couplers of our invention can be incorporated in photographic silverhalide emulsions with any of the wellknown uncolored cyan-formingcouplers such as the following:

any of the uncolored cyan forming couplers described in such U.S.patents as the following:

Inventor U.S. Patent Date of Issue 7 March 9, 1943.

April 4, 1944. November 14, 1944. January 16, 1945. February 20, 1945.June 28, 1949. March 11,1952. January 4, 1955.

March 22, 1955.

June 14, 1955.

December 27, 1955. November 27, 1956.

Salminen et al Vltturn et a1--. Weissberger- Do Godowsky OressmanParmerter Salru1nen Photographic emulsions containing our couplers maybe coated on transparent supports such as glass, cellulose esters, or ona non-transparent reflecting material such as paper or opaque celluloseester.

The novel magenta-colored cyan-forming couplers of our inventiondescribed hereinabove, have )\M of at least 500 my. and show unusuallylarge bathochromic shifts which make them valuable in color photography.These bathochromic shifts which are unexpected because of the relativelysmall chemical differences between our compounds and thenon-magenta-colored cyanforming compounds make the couplers of ourinvention particularly valuable for correcting the undesired green-lightabsorption of cyan dyes produced by color development. Ourmagenta-colored couplers produce upon color development, dyes that arecyan in color. This is a very significant advantage over prior artcouplers which are limited as to usefulness by the greenish cyan coloreddyes they produce upon color development. Our couplers can be used inany photographic emulsion where cyan couplers are used or can be used aswe have described. Although our couplers can be used alone in aphotographic silver halide emulsion, they are usually used in admixturewith uncolored cyan-forming couplers to obtain the color corection forwhich they are particularly valuable. Our magenta-colored couplers aremost useful in color photography, however they can also be used to dyeany other materials which are dyed with azo dyes.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

We claim:

1. A photographic silver halide emulsion containing a magenta-coloredcyan-forming coupler compound selected from the group consisting ofcompounds of the formula:

and

wherein X is an integer in the range of from 0 to 4; Y is an integer offrom 0 to 1; R is a member selected from the group consisting of alkylradicals containing from 6 to 15 carbon atoms, phenyl radicals,alkphenyl radicals in which the alkyl group contains from 1 to 15 carbonatoms, alkphenoxy radicals in which the alkyl group contains from 1 to15 carbon atoms, and alkphenoxyphenyl radicals in which the alkyl groupcontains from 1 to 15 carbon atoms; R is an alkyl group having from 1 to4 carbon atoms; and R is an alkyl group having 1 to 12 carbon atoms.

2. A photographic silver halide emulsion containing a magenta-coloredcyan-forming coupler of the formula:

wherein X is an integer of from 0 to 4; Y is an integer from 0 to 1; Ris a member selected from the class consisting of alkyl radicalscontaining from 6 to 15 carbon atoms, phenyl radicals, alkphenylradicals in which the alkyl group contains from 1 to 15 carbon atoms,alkphenoxy radicals in which the alkyl group contains from 1 to 15carbon atoms and alkphenoxyphenyl radicals in which the alkyl group hasfrom 1 to 15 carbon atoms; and R is an alkyl group having from 1 to 4carbon atoms.

3. A photographic silver halide emulsion containing a magenta-coloredcyan-forming coupler compound of the formula:

wherein X is an integer from 0 to 4; Y is an integer from 0 to 1; R is amember selected from the group consisting of alkyl radicals containingfrom 6 to 15 carbon atoms, phenyl radicals, alkphenyl radicals in whichthe alkyl group contains from 1 to 15 carbon atoms, alkphenoxy radicalsin which the alkyl group contains from 1 to 15 carbon atoms andalkphenoxyphenyl radicals in which the alkyl group contains from 1 to 15carbon atoms; and R is an alkyl group having from 1 to 12 carbon atoms.

4. A photographic gelatino silver halide emulsion containing1-hydroXy-4-(2acetylphenylazo)-N-[fi-(ZA-diterliary-amylphenoxy)butyl]-2-naphthamide.

5. A photographic gelatino silver halide emulsion containingl-hydroxy-4-(2-acetyl phenylazo) N [4(p-tertiary-butyl phenoxy)phenyl]-2-naphthamide.

-6. A photographic gelatino silver halide emulsion containing1-hydroxy-4-(3-carbethoxy 2 naphthylazo)-N- [4(2,4-di-tertiary-amplphenoxy)phenyl] -2-naphthamide.

7. A photographic gelatino silver halide emulsion containing 1hydroxy-4-(3-carbododecoxy-Z-naphthylazo)-N-[6-(2,4-di-n-amylphenoxy)butyl]-2-naphthamide.

'8. A photographic gelatino silver halide emulsion containing 1hydroxy-4-(3-carbethoxy-Z-naphthylazo-N-[6-(2,4-di-tertiary-amylphenoxy)butyl] -2-naphthamide.

9. A photographic silver halide emulsion containing, in combination, amagenta-colored cyan-forming coupler compound as defined in claim 1 andan uncolored cyanforming coupler which forms the same cyan dye as formedfrom the magenta-colored cyan-forming coupler upon coupling with thedevelopment product of a primary aromatic amino developing agent, saiduncolored coupler having the general formula:

wherein X is an integer of from to 4; Y is an integer from 0 to 1; and Ris a member selected from the group consisting of alkyl radicalscontaining from 6 to 15 carbon atoms, phenyl radicals, alkphenylradicals in which the alkyl group contains from 1 to 15 carbon atoms,alkphenoxy radicals in which the alkyl group contains from 1 to 15carbon atoms, alkphenoxyphenyl radicals in which the alkyl groupcontains from 1 to 15 carbon atoms.

110. A photographic silver halide emulsion containing in combination (a)a magenta-colored cyan-forming coupler compound selected from the classconsisting of those having the formula:

and those having the formula:

wherein X is an integer in the range of 0 to 4, Y is an integer from 0to 1; R is a member selected from the group consisting of alkyl radicalscontaining from 6 to 15 carbon atoms, phenyl radicals, alkphenylradicals in which the alkyl group contains from 1 to 15 carbon atoms,alkphenoxy radicals in which the alkyl group contains from 1 to 15carbon atoms, and alkphenoxyphenyl radicals in which the alkyl groupcontains from 1 to 15 carbon atoms; R is an alkyl group containing from1 to 4 carbon atoms; and R is an alkyl group containing from 1 to 12carbon atoms; and (b) an uncolored cyanforming coupler which forms a dyeupon coupling with the oxidation products of a primary aromatic aminodeveloping agent.

11. The method of producing a cyan dye image against a magenta dyebackground in a latent image bearing silver halide emulsion layercontaining an incorporated magentacolored cyan for-ming coupler of claim1 comprising the steps of developing said layer in a primary aromaticamino developer to produce a combined silver and cyan dye image againsta magenta dye and silver halide background and subsequently convertingthe silver to silver halide by bleaching, and then removing the silverhalide by fixing said layer.

12. The method of producing a cyan dye image against a magenta dyebackground in a latent irna'ge bearing gelatino-silver halide emulsionlayer containing the magentacolored cyan forming coupler l-hydroXy-4-(2-acetylphenylazo)-2-naphthanilide comprising the steps of developing saidlayer in a primary aromatic amino developer to produce a combined silverand cyan dye image against a magenta dye and silver halide backgroundand subsequently converting the silver to silver halide by bleaching,and then removing the silver halide by fixing said layer.

References Cited in the file of this patent UNITED STATES PATENTS1,975,611 Mendoza Oct. 2, 1934 2,521,908 Glass Sept. 12, 1950 2,584,349Heinrbach Feb. 5, 1952 2,706,684 Graham Apr. 19, 1955 2,725,291 GrahamNov. 29, 1955 2,756,225 Frisch July 24, 1956 FOREIGN PATENTS 140,359Hungary Nov. 15, 1950

1. A PHOTOGRAHIC SILVER HALIDE EMULSION CONTAINING A MAGENTA-COLOREDCYAN-FORMING COUPLER COMPOUND SELECTED FROM THE GROUP CONSISTING OFCOMPOUNDS OF THE FORMULA: